Versatile Para-Substituted Pyridine Lanthanide Coordination Complexes Allow Late Stage Tailoring of Complex Function

Matthieu Starck*, Jack D. Fradgley, Davide F. De Rosa, Andrei S. Batsanov, Maria Papa, Michael J. Taylor, Janet E. Lovett, Jacob C. Lutter, Matthew J. Allen, David Parker*

*Corresponding author for this work

Research output: Contribution to journalJournal articlepeer-review

6 Citations (Scopus)

Abstract

A series of cationic and neutral p−Br and p−NO2 pyridine substituted Eu(III) and Gd(III) coordination complexes serve as versatile synthetic intermediates. Nucleophilic aromatic substitution occurs readily at the para position under mild conditions, allowing C−N and C−C bond forming reactions to take place, permitting the introduction of azide, amino and alkynyl substituents. For Eu(III) complexes, this approach allows late stage tuning of absorption and emission spectral properties, exemplified by the lowering of the energy of an LMCT transition accompanied by a reduction in the Eu−Npy bond length. Additionally, these complexes provide direct access to the corresponding Eu(II) analogues. With the Gd(III) series, the nature of the p-substituent does not significantly change the EPR properties (linewidth, relaxation times), as required for their development as EPR spin probes that can be readily conjugated to biomolecules under mild conditions.

Original languageEnglish
Pages (from-to)17921-17927
Number of pages7
JournalChemistry - A European Journal
Volume27
Issue number71
Early online date27 Oct 2021
DOIs
Publication statusPublished - 20 Dec 2021

Scopus Subject Areas

  • Catalysis
  • Organic Chemistry

User-Defined Keywords

  • EPR
  • europium
  • gadolinium
  • luminescence

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